Bleaching composition

ABSTRACT

A BLEACHING COMPOSITION CONTAINING A BUILDER, DETERGENT, WATER-SOLUBLE HYDROGEN PEROXIDE ADDITION COMPOUND, AND A COPOLYMER OF A VINYL COMPOUND OF FORMULA RCH=CHR WHERE ONE R REPRESENTS A HYDROGEN ATOM AND THE OTHER R REPRESENTS AN ALKYL ETHER RADICAL HAVING ONE TO FOUR CARBON ATOMS OR A HYDROGEN ATOM. THE BLEACHING COMPOSITION HAS AN IMPROVED BLEACHING ACTION DUE TO THE REDUCED RATE OF ACTIVE OXYGEN LOSS FROM THE HYDROGEN PEROXIDE ADDITION COMPOUND IN THE AQUEOUS SOLUTION. THE REDUCTION IN THE RATE OF ACTIVE OXYGEN LOSS IS ACCOMPLISHED BY THE INCLUSION OF A MINOR AMOUNT OF THE COPOLYMER IN THE BLEACHING COMPOSITION.

3,563,443 Patented May 16, 1972 U.S. Cl. 252-99 10 Claims ABSTRACT OFTHE DISCLOSURE A bleaching composition containing a builder, detergent,Water-soluble hydrogen peroxide addition compound, and a copolymer of avinyl compound of formula RCH=CHR where one R represents a hydrogen atomand the other R represents an alkyl ether radical having one to fourcarbon atoms or a hydrogen atom. The bleaching composition has animproved bleaching action due to the reduced rate of active oxygen lossfrom the hydrogen peroxide addition compound in the aqueous solution.The reduction in the rate of active oxygen loss is accomplished by theinclusion of a minor amount of the copolymer in the bleachingcomposition.

The present invention pertains to a bleaching composition which isgenerally in granular or powdered form with improved bleachingperformance. Specifically, it pertains to a bleaching compositioncomprising a hydrogen peroxide addition compound, which decomposes uponcontact with water yielding hydrogen peroxide; and, a Water-solublecopolymer of maleic anhydride and a vinyl compound, or a water-solublesalt thereof. More specifically, this invention relates to a bleachingcomposition, having detergent properties comprising an organicsurface-active agent, a water-soluble inorganic builder, used alone orin combination with a water-soluble organic builder, a hydrogen peroxideaddition compound, and a water-soluble copolymer of maleic anhydride anda vinyl compound, or a water-soluble salt thereof.

It is known that the hydrogen peroxide addition compounds orperoxyhydrates, for example, sodium perborate, decompose in aqueoussolution, and rapidly release their active oxygen at high temperature,e.g. above about 80 C. Said rapid release of oxygen can damage textilematerials, and especially fine garments, embroidery, and the like; italso prevents an adequate and effective use of the available activeoxygen for bleaching purposes.

Many attempts have been made to control the rapid release of oxygen inaqueous solutions to avoid damage to textile materials, and to obtain anoptimum bleaching effect. Other attempts have been directed toinitiating the release of oxygen at temperatures below 80 C. by addingactivators. Monoacyl derivatives of hydantoin have been proposed forthis purpose in the British Pat. 965,672. German Pat. 271,155 teachescontrolling the release of oxygen of peroxyhydrates at about 80 to 85 C.by incorporating tin derivatives, while in U.S. Pats. 2,121,952 and2,141,189, alkali earth metal silicates are proposed for this purpose.And, in the German Pat. 721,317, the addition is suggested ofaminocarboxylic acids (or salts thereof) substituted in thealpha-position by more than one carboxyl radical.

The tin derivatives precipitate in aqueous solution as insoluble stannicoxide; the alkali earth metal silicates are only slightly soluble inwater; both may stain textile materials. The use of aminocarboxylicacids is inadequate because some of the peroxyhydrates decomposevigorously at or near boiling temperature when these acids are alsopresent in the aqueous solution.

By the present invention, a bleaching composition is provided whichpermits an effective control of the decomposition rate of the hydrogenperoxide in the aqueous solution, and an adequate use of the activeoxygen in the composition which, in turn, results in a better bleachingcontrol and regulation than heretofore possible.

These and other advantages will become apparent from the followingdescription of the invention.

Hydrogen peroxide addition compounds decompose in aqueous solution athigh temperatures yielding H 0 and salts. Said hydrogen peroxide in turndecomposes to release oxygen. The adequate use of the active oxygenaccording to the present invention is obtained by controlling thedecomposition rate of the hydrogen peroxide. The decomposition rate ofthe H 0 is also influenced by the pH of the solution, the alkali metalions, which are present, the temperature of the solution, the waterhardness and the container materials in which the bleaching isperformed.

It has now been found that the decomposition rate of the H 0 in anaqueous bleaching or bleaching and detergent solution, can be controlledif in the solution is present at small amount of a water-solublecopolymer of maleic anhydride and a vinyl compound of the formulaRCH=HCR, wherein one R represents a hydrogen atom and the other Rrepresents a C alkyl ether radical or a hydrogen atom, or awater-soluble alkali metal or ammonium salt of said copolymer.

Thus, the present invention pertains to a bleaching, or bleaching anddetergent composition comprising, by weight, from 0% to about 50% of asurface-active agent selected from the group consisting of anionic,amphoteric, zwitterionic and nonionic detergent, and mixtures thereof(or a non-cationic detergent); from about 10% to about of awater-soluble, inorganic builder salt, or mixtures thereof; from about0.1% to about 5% of active oxygen in the form of a water-solublehydrogen peroxide addition compound or mixtures thereof; and from about0.25% to about 10% of a water-soluble copolymer of a vinyl compound ofthe formula RCH=CHR wherein one R represents a hydrogen atom and theother R represents a C alkyl ether radical or hydrogen atom, and maleicanhydride, or a water-soluble alkali metal or ammonium salt of saidcopolymer.

Detergent and bleaching compositions, which are preferred, contain, byweight, from about 5% to about 20% of a non-cationic detergent, fromabout 15% to about 60% of an inorganic builder salt (preferably, sodiumtripolyphosphate), from about 0.5% to about 5% of active oxygen in theform of a water-soluble inorganic hydrogen peroxide addition compound,and from about 0.5% to about 5% of a water-soluble copolymer of a vinylcompound of the formula RCH=CH'R, wherein one R represents a hydrogenatom and the other R represents an OCH radical or a hydrogen atom, andmaleic anhydride, or water-soluble alkali metal or ammonium salt of saidcopolymer. Maleic anhydride-vinyl methyl ether is the most preferredcopolymer.

The detergent composition can have any of the several commerciallyavailable forms, for example, granular, powder, flake and tablet forms.The granular and powdered forms are preferred.

The degree of polymerization of the copolymer influences its watersolubility. It is difiicult, however, to establish an absolute value onthe upper and the lower limit of the degree of polymerization, which mayvary within a wide range. It is essential that the copolymer isadequately water-soluble under ordinary bleaching and washingconditions. There is a recognized correlation between the viscosities ofpolymeric compounds and their relative molecular weights or degrees ofpolymerization. 'Ihese viscosity figures are quite meaningful and theyare frequently more readily available than the molecular weights.Therefore, the copolymers described hereinafter are characterized eitherin terms of their specific viscosity or in centipoises. For eachcopolymer the most suitable term is given. 'For the maleicanhydride-vinyl ether C alkyl copolymers, the specific viscosity variespreferably between 0.1 and 6.0, most preferably between 0.2 and 5.0; thespecific viscosity is defined by measuring the viscosity of 1 g. of thecopolymer in 100 cc. methylethylketone in a Cannon Fenske viscositymeter at 25 C. The viscosity of the maleic anhydride-ethylene copolymervaries preferably between 1.2 and 100 centipoises when measured as anaqueous solution containing 2% of the copolymerthe solution beingadjusted to have a pI-I of about 10in a Brookfield RTV viscosity meterat 10 r.p.m. and at 25 C.

The hydrogen peroxide addition compounds, which are used in thecompositions of the invention are organic or, preferably, inorganic innature. A great variety of these compounds exists. Most of them areprepared by crystallization from solutions containing H Others areprepared by drying a slurry containing the corresponding salts and H 0The most important hydrogen peroxide addition compounds are theperborates, e.g. the sodium perborate monoand tetrahydrates. Otherperborates which can be used in the present invention are the potassiumand ammonium or true perborates having the formulae 2KBO H 0 and 2NH BO'H O, respectively. Other valuable hydrogen peroxide addition compoundsare the carbonate peroxyhydrates, e.g., 2Na CO -3H O and the phosphateperoxyhydrates. Although a great variety of sodium potassium, ammoniumand alkali earth metal phosphates can be used, sodium pyrophosphateperoxyhydrate (Na P O -2H O is preferred. The most suitable organichydrogen peroxide addition compound which can be used in the presentinvention is the urea peroxide (CO(N'H -H O because it is one of the fewfree flowing dry organic hydrogen peroxide addition compounds.

The following tests illustrate the effectiveness of the water-solublemaleic anhydride-vinyl methyl ether c0- polymers and maleicanhydride-ethylene copolymers in controlling the decomposition rate ofhydrogen peroxide, which is obtained by the decomposition of thehydrogen peroxide addition compounds in aqueous solutions.

Test A To five aqueous solutions (Water hardness 3.4 millimoles/1 Oa++and Mg++, ratio Ca++; Mg++ about 3:1) was added sodium perboratetetrahydrate, corresponding to 200 p.=p.m. active oxygen, and 0.5% byweight of a detergent composition consisting of of sodium alkylbenzenesulfonate (average C atoms of alkyl radical: 11.8), 2% of apolyoxyethylene-polyoxypropylene condensate (molecular weight ofpolyoxypropylene: 1750, polyoxyethylene: 80% by weight of total weightof condensate), 32%" of sodium tripolyphosphate, 6% of sodium silicate,2% of hydrogenated fish oil fatty acid (average molecular weight 285),6% of sodium sulfate, and 42% of moisture (all percentages by weight).

The first solution was used as a reference. To the second and thirdaqueous solution 1.0% and 5% respectively by weight, calculated on theweight of the detergent composition, of the Water-soluble maleicanhydride-vinyl methyl ether copolymer were added. And to the fourth andfifth aqueous solution 1.0% and 5% respectively by weight, based on theweight of the detergent composition, of the water-soluble maleicanhydride-ethylene copolymer were added.

Each aqueous solution was heated to and maintained at 92 C. The activeoxygen was determined after 5, 10,

15 and 20 minutes by the permanganate method. (See, for details,Quantitative Inorganic Analysis, by A. Vogel, third edition, 1962,Longmans, London, page 295; but whereby 50 cc. of a sample solution wasacidified with 50 cc. of sulfuric acid (0.1 N), and titrated with a 0.1N solution of KMnO until permanent pink; 1 cc. KMnO =16 p.p.rn. ofactive oxygen). The results are presented in Table I.

1 Percentage by weight of copolymer calculated on weight of detergentcomposition.

2 Specific viscosity about 0.4 (1 g. in 100 cc. methylethylketone at 250.); ratio of monomers 1:1. 1 :Visoosity, 2 cps. in 2% aqueous solutionat 25 0.; ratio of monomers Test B The efl'ectiveness of thosecopolymers when compared with a strong sequestering agent, such as, forexample, ethylenediaminetetraacetic acid (EDTA) is shown in Table II. Toemphasize the effect, seven solutions were prepared with deionizedwater, containing 1 ppm. of Fe+++ ions, and 0.5% by weight of thedetergent composition dcscribed in Test A. Each solution was heated toand maintained at 92 C. To each solution was then added sodium perboratetetrahydrate, corresponding to 200 p.p.m. of active oxygen, and at thesame time 1.0% and 5% respectively by weight, based on the weight of thedetergent composition, of ethylenediaminetetraacetic acid to solutions 2and 3, of maleic anhydride-vinyl methyl ether copolymer to solutions 4and 5, and of maleic anhydride-ethylene copolymer to solutions 6 and 7.The active oxygen available at 5, 10, 15, and 20 min. was determined bythe permanganate method for solutions 1, 4, 5, 6 and 7, and by thethiosulfate method for the solutions containing EDTA. (Thiosulfatemethod: a 10 cc. sample solution is acidified with sulfuric acid 1.0 N;30 cc. of a 15% IK solution-H00 cc. distilled Water is added, and thewhole is stirred; after 10 minutes in the dark it is titrated with 0.01thiosulfate; when yellow color fades, 0.5 g. starch is added andtitration continued until colorless solution is obtained.)

TAB LE II Percent of active oxygen available 9. er Percent Solu- H202decomposition by 10 15 20 tion controlling agent weight 1 min. min. min.min.

0 56 46. 5 50 1 66 54. 5 45. 5 33 A 5 73. 5 61. 5 51 35. 5 4 Maleicanhydride- 1 56 46 39 vinyl methyl ether copolymer. 5 .dofl 5 83 76. 572 66. 5 6 Maleic anhydride- 1 79 65. 5 56 48 ethylene copolymer! 7 "do!5 86 86 83. 5 80. 5

1 Percentage by weight of decomposition controlling agent, calculated onthe weight of detergent composition.

2 Specific viscosity, about 0.4; ratio of monomers 1:1. 3 Viscosity, 2cps. in 2% aqueous solution at 25 0.; ratio of monomers :1.

Comparing the percentages of available active oxygen in Table II, EDTAat 1% concentration seems to enhance the decomposition of the hydrogenperoxide addition compound, while the difference in available activeoxygen be- 6 which Cu++ ions and Fe ions were added. The concentrationof the bleaching and detergent composition, specified hereinafter, ineach solution was 0.6% by weight. The pH of said aqueous solutions wasabove 8.5.

tween solutions with and without 5% EDTA after 20 min. 5 The followingcompositions (Table IV) were tested (figis insignificant. The ditferencein available active oxygen ures are percent by weight) in aqueoussolutions containin the solution containing 5% of maleicanhydride-ethyling 0.5 p.p.m. of Cu++ ions and 0.5 p.p.m. of Fe ions.ene copolymer and the control solution after 20 minutes TABLE 1V is morethan 40%. C m I H III IV T65t C 10 ompos on. V VI Suiat t 10 10 10 Tocompare the effectiveness as H 0 decompos1t1on m 45 45 45 i i8 i3controlling agent in aqueous solutions of maleic anhydrideggg g gg f g gg 3 ethylene copolymer over maleic anhydride polymer, five Balance 5 105 20 i i tests as described in the section Test B were run. But 15Surfactant, consisting of: instead of Fe ions, the test solutionscontained 1 p.p.m. (a) 65.57 by welgltttzf a sfdilfinlstraiilghtthagnalkyl benzene sulfona e average a ms n a y la ca 11.8 of Cu The activeOxygen avallable at 15 (b) 21% by weight of hydrogenated fish 011(average molecular and min. was determined by the permanganate method:weiglht m) i ht f t u I h c 13.5 y weg o a a ow aco ol-ethylenc oxidecondensate, The results are presented 1n Table III. (avegage oxide units11) T ABLE In except for compositions V and VI, wherein the surfactantis the Na 20 3-(tI; I,N-dimethy1-N-coconutalkylammonio)-2-hydroxypropane-1-sulfo- Percent of active oxygenavailable after- 2 Builder Percent (a) Examples I and II, sodiumpyrophosphate 501w H202 decomposition by 5 10 15 20 (b) ExgrsntaliesIlltalilmli IVE1 ia 3:i1nn%ix;ture of 1sodium tripolyphosphate 1 an 0111718 yene am oeraaceae tron controlling agent weight min. min. min.min (0) Examples V and VI Sodium tripolyphosphate 1 o 37 23 5 13 25 3Peroxyhydrate, sodium perborate tetrahydrate. 2 M51910 anhydride 1 56538 28 215 4 Copolymer, a 1:1 maleic anhydride-vinyl methyl ether, havinga ethylene l y 3151s??? viscosity of 0.4 (1 gram in 100 cc.methylethylketone solution at 3 33%; 5 74.5 60 5 55 465 Balance, sodiumsulfate. 4 ifi f igki 1 28 21 The percentages of active oxygen availableafter 10 and 5 do. 5 55 35.6 27.5 21. 20 minutes in the aqueoussolutions maintained at 92 C., 1 Percentage by weight of decompositioncontrolling agent calculated measured accol'dmg to the usualpermanganate mahod, on the weight of detergent composition.

2 Specific viscosity about 0.4; ratio of monomers 1:1. 3 Viscosity, 2cps. in 2% aqueous solution at 25 0. TABLE V According to Table III,solution 1, copper ions Cu++ 35 Cmmsitmn" enhance the hydrogen peroxidedecomposition. The de- Time I II III IV V VI COInpOSltlOH COlltl'OHlDgefiect of t Ill-3161c allhydrlde 10 minutes 50 79 5 77 2 80 polymer israther small when compared with the effect ob- 20 minutes 34 73 49 e7 1075 tained b the maleic anhydride-ethylene copolymer, since thepercentages of available active oxygen of solution 5 are 40 Th6efiectlveness 0f the malelc y yl m hyl lower than those of solution 2,either after 5, 10, 15 or 20 ether QP Y 1n the s ut ons II, IV and VI isevident minutes, notwithstanding the higher amount of polymer from SaldTable present. Test E Test D The scope of the lnvention, and thesurprising results The surprising efiect of the copolymers of maleicanhycan also be seen from the following series of tests (Tables dude anda vinyl compound as defined hereinbefore, in de- VI and VII), wherebythe active oxygen available was tergent solutions contaimng hydrogenperoxide addition measured after 20 minutes according to the usualpercompounds is also apparent from the following tables. manganatemethod. The concentration of the detergent Sodium perborate tetrahydratestability is extremely sencomposition specified below is 0.6% by weight,the temsitive to pH increase, and especially in the range 8.5-9.0perature of the solutions 92 C., and the water is deand above. It isalso known that the decomposition rate ionized water into which Cu++and/or Fe+++ ions were of H 0 increases with increasing pH, and iscatalyzed by added.

TABLE VI Composition VII VIII IX X XI XII XIII XIV XV XVI Suriactant 1010 10 25 25 2s 10 10 a5 35 Builder so 60 35 35 a5 45 45 45 45Peroxyhydratek 20 20 20 30 30 30 35 35 10 1o Copolymer 0 3 7 0 3 7 0 5 02 Balance 5 10 7 3 1O 7 3 10 5 10 8 1 Surfactant, as Examples I-IV ofTable IV.

2 Builder, sodium tripolyphosphate.

3 Peroxyhydrate, sodium perborate tetrahydrate.

4 Copolymer, a 1:1 maleie anhydride-vinyl methyl ether copolymer havinga specific viscosity of 0 4 5 Balance; sodium sulfate.

copper and iron ions. To simulate said Worse conditions, aqueoussolutions were prepared of deionized water, into The percent of activeoxygen available after 20 min. at 92 C. is:

The surprising effectiveness in controlling the H decomposition rate bythe copolymer is evident when comparing the results of composition VIIwith VIII and IX, or composition X with XI and XII, or XIII with XIV,and XV with XVI.

The surface active agents which can be used in the compositions of thepresent invention includes: anionic, amphoteric, zwitterionic, andnonionic detergent and mixtures thereof. These suitable substances areenumerated below.

(a) Anionic detergent which can be used in the compositions of thisinvention include both soap and nonsoap detergent compounds. Examples ofsuitable soaps are the sodium, potassium, ammonium and alkylammoniumsalts of higher fatty acids (C -C Examples of anionic organic non-soapdetergent compounds are the watersoluble alkali metal salts or organicsulfuric reaction products having in their molecular structure an alkylradical containing from about 8 to about 22 carbon atoms and a radicalselected from the groups consisting of sulfonic acid and sulfuric acidester radicals. (Included in the term alkyl is the alkyl portion ofhigher acyl radicals.) Important examples of the synthetic detergentswhich form a part of the compositions of the present invention are thesodium or potassium alkyl sulfates, especially those obtained bysulfating higher alcohols (Cg-C1 carbon atoms); sodium or potassiumalkyl benzene sulfonates, such as are described in U.S. Pats. 2,220,009and 2,477,- 383, in which the alkyl group contains from about 9 to aboutcarbon atoms; sodium alkyl glyceryl ether sulfonates especially thoseethers of the higher alcohols derived from tallow and coconut oil;sodium coconut oil fatty acid monoglyceride sulfates and sulfonates;sodium or potassium salts of sulfuric acid esters of the reactionproduct of one mole of a higher fatty alcohol (e.g. tallow or coconutoil alcohols) and about 1 to 6 moles of ethylene oxide; sodium orpotassium salts of alkyl phenol ethylene oxide ether sulfate with about1 to about 10 units of ethylene oxide per molecule and in which thealkyl radicals contain about 9 to about 12 carbon atoms; the reactionproduct of C1042 fatty acids with taurines or isethionic acid andneutralized with sodium hydroxide; and others known in the art, a numberbeing specifically set forth in US. Pats. 2,486,921; 2,486,922 and2,396,278.

(b) Nonionic synthetic detergents may be broadly defined as compoundsaliphatic or alkylaromatic in nature which do not ionize in watersolutions. For example, compounds formed by condensing ethylene oxidewith a hydrophobic base formed by the condensation of propylene oxidewith propylene glycol, whereby the hydrophobic portion of the moleculehas a molecular weight of from about 1,500 to 1,800, and thepolyoxyethylene content is about 50% of the total weight of thecondensation product Other suitable nonionic synthetic detergentsinclude:

(1) The polyethylene oxide condensates of alkyl phenols, e.g., thecondensation products of alkyl phenols having an alkyl group containingfrom about 6 to 12 carbon atoms, with ethylene oxide, the said ethyleneoxide being present in amounts equal to 10 to 25 moles of ethylene oxideper mole of alkyl phenol.

(2) Those derived from the condensation of ethylene oxide with theproduct resulting from the reaction of propylene oxide andethylenediamine. For example, compounds containing from about 40% toabout 80% polyoxyethylene by weight and having a total molecular weightof from about 5,000 to about 11,000 resulting from the reaction ofethylene oxide groups with a hydrophobic base constituted of thereaction product of ethylene diamine and excess propylene oxide, saidhydrophobic base having a molecular weight of the order of 2,500 to3,000 are satisfactory.

(3) The condensation product of C1042 aliphatic alcohols having from 8to 18 carbon atoms, with from 10 to 30 moles of ethylene oxide per moleof alcohol.

(4) Long chain tertiary amine and phosphine oxides corresponding to thefollowing general Formula wherein X represents a nitrogen or phosphorusatom, R is an alkyl radical of from about 8 to 18 carbon atoms, and Rand R are each methyl or ethyl radicals. The arrow in the formula is aconventional representation of a semi-polar bond. Examples of suchoxides suitable for use in this invention include dimethyldodecylamineoxide, and dimethyloctylamine oxide, dimethyldodecylphosphine oxide, andethylmethyltetradecylphosphine oxide.

(5) Dialkyl sulfoxides corresponding to the following formula RRS- 0,wherein R is an alkyl, alkenyl, betaor gamma-monohydroxyalkyl radical oran alkyl or betaor gamma-monohydroxyalkyl radical containing one or twoother oxygen atoms in the chain, the R groups ranging from 10 to 18carbon atoms in chain length, and wherein R is methyl or ethyl. Examplesof suitable sulfoxide compounds are: dodecyl methyl sulfoxide and3-hydroxytridecyl methyl sulfoxide.

(c) Ampholytic synthetic detergents can be broadly described asderivatives of aliphatic secondary and tertiary amines, in which thealiphatic radical may be straight chain or branched and wherein one ofthe aliphatic substituents contains from about 8 to 18 carbon atoms andone contains an anionic water solubilizing group. Examples of compoundsfalling within this definition are sodium-3-dodecylaminopropionate andsodium-3-dodecylaminopropanesulfonate.

(d) Zwitterionic synthetic detergents can be broadly described asderivatives of aliphatic quaternary ammonium compounds in which thealiphatic radical may be straight chain or branched and wherein one ofthe aliphatic substituents contains from about 8 to 18 carbon atoms andone contains an anionic water solubilizing group. Examples of compoundsfalling within this definition are3-(N,N-dirnethyl-N-hexadecylammonio)propanel-sulfonate and3-(N,N-dimethyl-N-hexadecylammonio)- 2-hydroxypropane-l-sulfonate whichare especially preferred for their excellent detergency characteristics.

The anionic, nonionic, ampholytic and zwitterionic detergents mentionedabove can be used singly or in combination in the practice of thepresent invention. The above examples are merely specific illustrationsof the numerous detergents which can find application within the scopeof this invention.

The builders which can be used in the compositions of the presentinvention include the water-soluble inorganic alkaline builder salts,used as such or in combination with organic alkaline builder salts.Suitable inorganic builder salts are the soluble polyphosphate saltssuch as sodium or potassium pyrophosphate and tripolyphosphate, furthersodium silicate, sodium carbonate and sodium borate. Suitable organicbuilder salts are the sodium and potassium ethylenediaminetetraacetatesand nitriloacetates, the sodium and potassium lower alkyl diphosphonatessuch as trisodium ethylene-l-hydroxy-l,l-diphosphonate, the alkali metalsalts of phytic acids such as sodium phytate, and mixtures of saidinorganic and organic builder salts.

The detergent compositions contain preferably a builder and a detergentin the weight ratio of about 1:3 to about 10: 1. The preferred ratio ofbuilder to detergent is about 1:2 to about 5:1.

In a finished detergent formulation of this invention there will oftenbe added minor amounts of materials which make the product moreattractive. The following are mentioned by way of example. Sodiumcarboxymethyl cellulose (hereinafter designated as CMC) can be added inminor amounts to inhibit soil redeposition. A tarnish inhibitor such asbenzotriazole or ethylenethiourea can also be added in amounts up toabout 2%. Fluorescers, perfume and color, while not essential in thecompositions of the invention, can be added in small amounts. Analkaline material or alkali such as sodium hydroxide or potassiumhydroxide can be added in minor amounts as supplementary pH adjusters.There might also be mentioned as suitable additives: bacteriostats,sodium sulfate, and sodium carbonate and bactericides.

Corrosion inhibitors generally are also added. Soluble silicates arehighly effective inhibitors and can be added to certain formulas of thisinvention at levels of from about 3% to about 8%. Alkali metal,preferably potassium or sodium, silicates having a weight ratio of SiO:M O of from 1:1 to 28:1 can be used. M in this ratio refers to sodiumor potassium. A sodium silicate having a ratio of Si :Na O of about1.6:1 to 2.45 :1 is especially preferred for economy and effectiveness.

In view of the increasing acceptance by the general public of builtdetergent compositions with oxygen bleaching agents for virtually allwashing and cleaning situations especially laundering, it is a verysignificant contribution of this invention that an improved detergentproduct is made possible that will provide bleaching levels superior toa normally built product, because of the adequate use of the activeoxygen in the bleaching and washing liquor, while the copolymersinfluence the whiteness maintenance properties of the washing solutionspositively.

The following examples serve to illustrate, but not to limit the novelcompositions of the present invention. All percentages in the examplesare by weight.

EXAMPLE I A granular bleaching and detergent composition describedbelow, is prepared by slurrying the surfaceactive agents and builders,spray-drying the slurry, and mixing the perborate, copolymer and perfumewith the spray-dried product. The end product consists of:

12% sodium alkylbenzene sulfonate (average chain length hydrogenatedfish oil fatty acids (average mol. wt.

3% tallow alcohol-ethylene oxide (average ethylene units 35 sodiumtripolyphosphate 5% sodium silicate 3% maleic anhydride-vinyl methylether copolymer (specific viscosity, about 0.4)

30% sodium perborate tetrahydrate balance: sodium sulfate, CMC, perfume,moisture The maleic anhyride-viuyl methyl ether copolymer (ratio ofmonomers 1:1) can be replaced by the maleic anhydride-ethylene copolymerat an equal percentage basis, or by the disodium salts of one or both ofthem.

The sodium perborate tetrahydrate can be replaced on an equal percentagebasis by the carbonate peroxyhydrate, 2Na CO 3H O or by the sodiumpyrophosphate peroxyhydrate N21 P O -2H O EXAMPLE II A detergentcomposition was prepared by slurrying the detergent and builders,spray-drying the slurry, and adding the copolymer, perfume and perborateto the spraydried product. The finished product consisted of:

6% sodium 3 ,(N,N-dimethyl-N-tetradecylammonio)-2-hydroxypropane-l-sulfonate,

40% sodium tripolyphosphate,

25 sodium perborate tetrahydrate,

15 sodium sulfate, moisture, perfume,

5% maleic anhydride-vinyl methyl ether copolymer (specific viscosity,0.4),

9% sodium silicate.

The percentage of active oxygen available in a washing solution,containing 0.5% by weight of said detergent composition, heated at 92C., was, according to the usual permanganate method, after 10 minutes,77%, and after 20 minutes, 65%

Heavily soiled clothes, washed for 30 minutes with a solution of saiddetergent composition, were thoroughly cleaned and bleached.

Other suitable compositions are:

EXAMPLE III 6% of C1143 alkylbenzene sulfonate (Na salt),

3% of tallow alkyl sulfate (Na salt),

4% of polyoxyethylene polyoxypropylene condensate (molecular weight ofpolyoxypropylene 1750; polyoxyethylene 60% by weight),

2% of hydrogenated fish oil fatty acid (ave. mol. wt.

40% of sodium pyrophosphate,

30% of sodium perborate tetrahydrate,

5 of maleic anhydride-ethylene copolymer,

10% of sodium sulfate, moisture, CMC brightener.

EXAMPLE IV 5% of tallow alcohol-ethylene oxide condensate (average oxideunits 11),

2% of hydrogenated fish oil fatty acid (ave. mol. Wt. 285),

40% of sodium tripolyphosphate,

30% of sodium perborate tetrahydrate,

2% of maleic anhydride-vinyl methyl ether,

16% of sodium sulfate,

5% of perfume, sodium silicate, moisture.

EXAMPLE V 8% of sodium C alkylbenzene sulfonate,

4% of polyoxyethylene polyoxypropylene condensate (molecular weight ofpolyoxypropylene 1750; polyoxyethylene by weight),

27% of sodium tripolyphosphate,

8% of sodium pyrophosphate,

20% of sodium pyrophosphate peroxyhydrate,

2% of maleic anhydride-vinyl methyl ether copolymer,

6% of sodium silicate,

25% of sodium sulfate, and minor amounts of CMC, perfume.

EXAMPLE VI 5% of Na salt of C1248 fatty acids,

10% of nonylphenol-ethylene oxide condensate (average oxide units, 8),

40% of sodium tripolyphosphate,

25 of sodium perborate tetrahydrate,

5% of maleic anhydride-vinyl methyl ether,

balance (sodium sulfate, moisture, sodium silicate, CMC).

The foregoing description and examples describe and illustrate certainoperable and preferred embodiments of the present invention. It is notintended that the invention should be so limited since variations andmodifications thereof will be obvious to those skilled in the art, allof which are within the spirit and scope of this invention.

What is claimed is:

1. A bleaching composition containing a minor portion of a copolymer ofa vinyl compound and maleic anhydride or the corresponding alkali metalor ammonium salt of said copolymer, consisting essentially of:

(a) from 0% to about 50% by weight of a surfaceactive agent selectedfrom the group consisting of water-soluble anionic, amphoteric,zwitterionic and nonionic detergents, and mixtures thereof;

(b) from about 10% to about 80% by weight of a water-soluble inorganicbuilder salt, or mixtures thereof, alone or in combination with awater-soluble organic builder salt, or mixtures thereof;

(0) from about 0.1% to about 5% by weight of active oxygen, in the formof a Water-soluble hydrogen peroxide addition compound selected fromperborates, carbonate peroxyhydrates, phosphate peroxyhydrates, and ureaperoxide; and

(d) as said minor portion from about 0.25% to about 10% by weight of awater-soluble copolymer of:

(1) a vinyl compound having the general formula RCH=CHR, wherein one Rrepresents a hydrogen atom, and the other R represents a C alkyl etherradical or a hydrogen atom, and

(2) maleic anhydride, or the corresponding alkali metal or ammonium saltof said copolymer, wherein said copolymer has a monomer ratio of vinylcompound and maleic anhydride of about 1:1 and has a specific viscositybetween 0.1 and 6.0 when one R represents a C alkyl ether and aviscosity between 1.2 centipoises and 100 centipoises when each Rrepresents a hydrogen atom.

2. The composition according to claim 1, consisting essentially of:

(a) from about 5% to about 20% by weight of a surface-active agentselected from the group consisting of water-soluble anionic, amphoteric,zwitterionic and nonionic detergents, and mixtures thereof;

(b) from about 15% to about 60% of an inorganic builder salt;

() from about 0.5% to about by wt. of active oxygen, in the form of awater-soluble inorganic hydrogen peroxide addition compound, and

(d) from about 0.5% to about 5% by wt. of a watersoluble copolymer of:

(1) a vinyl compound of the general formula RCH==CHR, wherein one Rrepresents a hydrogen atom and the other R represents a -OCHZ radical ora hydrogen atom, and

12 (2) maleic anhydride, or the corresponding alkalimetal or ammoniumsalt thereof.

3. The composition according to claim 2 in which the surface-activeagent is an anionic detergent.

4. The composition according to claim 3 in which the surface-activeagent is a reaction product of sulfuric acid and C1048 fatty alcohols orC alkylbenzenes, and the alkali metal salt thereof.

5. The composition according to claim 2 in which the surface-activeagent is a nonionic detergent.

6. The composition according to claim 2 in which the surface-activeagent is a zwitterionic detergent.

7. The composition according to claim 2 in which the active oxygen ispresent as sodium perborate tetrahydrate.

8. The composition according to claim 2 in which the active oxygen ispresent as sodium pyrophosphate peroxyhydrate.

9. The composition according to claim 2 in which the builder salt issodium tripolyphosphate.

10. The composition according to claim 2 in which said copolymer is amaleic anhydride-vinyl methyl ether copolymer.

References Cited UNITED STATES PATENTS 3,308,067 3/1967 Diehl 252-1613,454,500 7/ 1969' Lancashire 25299 3,507,937 4/1970 Zirnmerer 252-99 XMAYER WEINBLATI, Primary Examiner US. Cl. X.R.

